JPH0641023A - Production of polyethylenepolyamine - Google Patents

Abstract

PURPOSE:To provide the method for efficiently preventing the generation of cyclic compounds and an alkylpyrazine in the method for producing the polyetylenepolyamine from ethanolamine as a raw material. CONSTITUTION:When the polyethylenepolyamine is produced from ethanolamine and ethyleneamine, the ethanolamine is dividedly fed into the reaction zone to provide the polyethylenepolyamine having a high quality.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing polyethylene polyamine. Polyethylene polyamine is a useful aliphatic amine compound used as a chelating agent, an epoxy curing agent, a wet strength agent, a lubricating oil additive and the like.

[0002]

2. Description of the Related Art A method for producing polyethylene polyamine from ethylene dichloride and ammonia is known. This method is widely practiced, and it is possible to produce a polyethylene polyamine having a small amount of cyclic substances such as piperazine, but a large amount of salt is produced as a by-product, and thus the separation and treatment are expensive. Have.

As a method of not producing salt as a by-product, a method of using ethanolamine as a raw material is known. Although a method for producing polyethylene polyamine from ethanolamine and ammonia in the presence of hydrogen and a hydrogenation catalyst has been widely practiced, many cyclic compounds such as piperazine are produced. In general, polyethylene polyamine is higher in quality when it does not contain a cyclic compound, so this method cannot be said to be an efficient method for producing polyethylene polyamine.

A method using an acid catalyst is also known as a method for producing a polyethylene polyamine using ethanolamine as a raw material. In this method, ethanolamine and ethyleneamine are dehydrated and condensed in the presence of an acid catalyst. It is known to use niobium-containing substances and phosphorus-containing substances as catalysts. This method makes it possible to produce polyethylene polyamine with less cyclics than when a hydrogenation catalyst is used. However, it has a drawback that a large amount of alkylpyrazine other than polyethylene polyamine is produced. In addition, in order to reduce the number of cyclics, it is necessary to increase the ethyleneamine / ethanolamine ratio of the raw material, but increasing the ethyleneamine / ethanolamine ratio increases the amount of unreacted ethyleneamine, which increases the cost of recycling the raw material. There is a problem of increasing productivity and decreasing productivity,
On the contrary, if the ethyleneamine / ethanolamine ratio is lowered in order to reduce the raw material recycling cost or improve the productivity, there is a drawback that the production amount of the cyclic compound increases and the quality of the polyethylene polyamine deteriorates. Therefore, this method cannot be said to be an efficient manufacturing method.

[0005]

As described above, many methods for producing polyethylene polyamine have been disclosed, but these methods are still inadequate from an industrial point of view.

Since the production method using ethanolamine as a raw material cannot efficiently suppress the formation of cyclic compounds and alkylpyrazine, despite the problem of by-product salt, polyethylene dichloride is mainly used as a raw material. Polyamines are manufactured.

[0007] Therefore, in the production method using ethanolamine as a raw material, which is free from the problem of by-product salt, it is desired to develop a method for efficiently suppressing the cyclic compound and alkylpyrazine.

[0008]

In view of this situation, the inventors of the present invention have made earnest studies on a method for producing ethanolamine and polyethylenepolyamine using ethyleneamine as a raw material, and as a result, dividedly supply ethanolamine to the reaction zone. According to the present invention, the novel fact that the cyclic compound and the alkylpyrazine in the polyethylene polyamine can be reduced without increasing the raw material recycling cost or decreasing the productivity was found, and the present invention was completed. .

That is, the present invention is a method for producing a polyethylene polyamine from ethanol amine and ethylene amine, characterized in that ethanol amine is dividedly supplied to the reaction zone.

The raw materials used in the method of the present invention are ethanolamine and ethyleneamine. In addition to these, it is also possible to use ammonia as a raw material.

In the method of the present invention, ethanolamine means a compound having an ethylene chain, an amino group and a hydroxyl group in the molecule, such as monoethanolamine, diethanolamine, triethanolamine, N- (2-aminoethyl) ethanolamine, N- (2-hydroxyethyl)
Examples thereof include piperazine. Ethyleneamine refers to a compound having amino groups at both ends of an ethylene chain, and examples thereof include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, piperazine, and N- (2-aminoethyl) piperazine. It Polyethylene polyamine refers to one having a plurality of ethylene chains among ethylene amines, and examples thereof include diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, piperazine, and N- (2-aminoethyl) piperazine. .

In the process of the present invention, ethanolamine is dividedly fed to the reaction zone. The reaction zone means a place where ethanolamine and ethyleneamine can react.
That is, supplying ethanolamine to the reaction zone means supplying ethanolamine to a place where ethanolamine and ethyleneamine can react. It is not necessary for ethanolamine and ethyleneamine to react at the time of supplying ethanolamine, and it is sufficient to pass through a portion where ethanolamine and ethyleneamine may react after supplying ethanolamine. In other words, ethanolamine does not necessarily have to be supplied to the part where the catalyst is present or the part at the reaction temperature, and at the time when ethanolamine is supplied, even if the catalyst is not present or is not at the reaction temperature, the Ethanolamine may be supplied to a portion where the supplied ethanolamine may pass through the existing portion or the portion at the reaction temperature.

In the method of the present invention, there is no particular limitation as long as the number of divided feeds of ethanolamine is two or more. However, if the number of divided feeds is too large, there arises a problem that the apparatus and equipment become complicated, and if the number of divided feeds is small, the quality improvement effect of the produced polyethylene polyamine becomes small. Therefore, when carrying out the method of the present invention, it is necessary to set the optimum number of divided feeds according to the purpose.

In the method of the present invention, the ratio of ethanolamine and ethyleneamine to be fed is as follows. In terms of the ratio of ethyleneamine to the total amount of ethanolamine supplied, the ethyleneamine / ethanolamine ratio is 0.5 to 10 in molar ratio. When the ethyleneamine / ethanolamine ratio is less than 0.5, the quality of polyethylene polyamine deteriorates because the amount of cyclics such as piperazine increases, and when the ethyleneamine / ethanolamine ratio exceeds 10, unreacted ethyleneamine increases. Therefore, cost is required for the separation and recovery.

In the method of the present invention, it is difficult to limit the divided supply amount of ethanolamine because it is greatly affected by the number of divisions. Further, the amount of ethanolamine to be supplied does not need to be evenly divided, and it does not matter if the first supply amount and the second supply amount are different.

The method of the present invention may be carried out in a batch system, a semi-batch system or a flow system, but is generally carried out by a low-cost flow reaction.

In the method of the present invention, the reaction is carried out using a catalyst. Usually, a phosphorus-containing substance, a niobium-containing substance or the like can be used as a catalyst, but other catalysts can be used. Further, it is not necessary to separately supply ethanolamine to the same catalyst. For example, ethanolamine supplied first time can be reacted with a phosphorus-containing catalyst and ethanolamine supplied second time can be reacted with a niobium-containing catalyst. .

In the method of the present invention, the reaction temperature varies depending on the kind of the catalyst, so that it is difficult to limit the reaction temperature.
It is 200 ° C. or higher and 400 ° C. or lower. The reaction temperature does not have to be constant, and it is possible to react the ethanolamine supplied at the first time at 250 ° C and the ethanolamine supplied at the second time at 300 ° C.

In the method of the present invention, the reaction may be carried out in a liquid phase or a gas phase, but the reaction in the liquid phase can produce a high quality polyethylene polyamine. However, even when the reaction is carried out in the gas phase, the quality of the polyethylene polyamine can be improved by dividingly supplying ethanolamine.

[0020]

INDUSTRIAL APPLICABILITY The present invention provides a method for producing a high-quality polyethylene polyamine containing a small amount of a cyclic compound and alkylpyrazine and is industrially extremely useful.

[0021]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

For the sake of brevity, ethyleneamine,
Ethanolamine is abbreviated by the following symbols.

EDA ethylenediamine MEA monoethanolamine PIP piperazine AEP N- (2-aminoethyl) piperazine HEP N- (2-hydroxyethyl) piperazine DETA diethylenetriamine AEEA N- (2-aminoethyl) ethanolamine TETA triethylenetetramine (direct) Chain, branched, cyclic isomer) TEPA Tetraethylenepentamine (linear, branched, cyclic isomer) PEHA Pentaethylenehexamine (linear, branched, cyclic isomer) Non-cyclic In order to show the body ratio, TE
The TA acyclic ratio was determined. TETA acyclic ratio = (linear TETA + branched TET
A) / (straight chain TETA + branched TETA + cyclic TET
A) × 100 Example 1 Two stainless annular reactors were prepared in which 60 ml of a catalyst (having 20% by weight of niobium oxide supported on alumina) was filled. One is designated as reactor A and the other is designated as reactor B. Then, when mixed with a raw material (referred to as raw material 1) having an EDA / MEA ratio of 4 (molar ratio) and the raw material 1, the EDA / MEA ratio was 2
An amount of MEA (referred to as raw material 2) which is (molar ratio) was prepared. Raw material 1 was supplied to the reactor A. Reaction temperature is 300
° C., the reaction pressure was 50 kg / cm ^2. Analysis of the reaction liquid leaving the reactor A showed that the MEA conversion rate was 41.3%.
Met. The raw material 2 was added to this reaction liquid, and it supplied to the reactor B. Reaction temperature is 300 ° C, reaction pressure is 50 kg / cm
^{It was set to 2} . When the reaction solution leaving the reactor B was analyzed, M
The EA conversion was 41.1% (total MEA conversion). The production ratio of the polyamine excluding the raw material and the produced water is as follows: PIP: 2.66 wt%, DETA: 55.95 wt%, AEEA: 3.70 wt%, AEP: 1.80 wt%, HEP: 0.00 % By weight, TETA; 17.60
% By weight, TEPA: 4.49% by weight, PEHA: 1.7
It was 5% by weight. The production amount of alkylpyrazine was 1.30%, and the acyclic ratio of TETA was 94.82% with respect to all polyamines.

Comparative Example 1 The same reactor and catalyst as in Example 1 were prepared. A raw material having an EDA / MEA ratio of 2 was supplied to the reactor A, and the reaction liquid discharged from the reactor A was directly supplied to the reactor B. At this time, the reaction temperature was 300 ° C., the reaction pressure was 50 kg / cm ^2, and M
The liquid hourly space velocity was adjusted so that the EA conversion rate was 41.1%. When the reaction liquid exiting the reactor B was analyzed, the production ratio of polyamine excluding the raw material and the produced water was PIP: 2.
70% by weight, DETA: 51.53% by weight, AEEA:
4.61% by weight, AEP: 2.01% by weight, HEP:
0.00 wt%, TETA; 14.21 wt%, TEP
A: 4.89% by weight, PEHA: 2.10% by weight. The production amount of alkylpyrazine was 1.58% with respect to the total polyamine, and the acyclic ratio of TETA was 93.
It was 44%.

Example 2 The same reactor and catalyst as in Example 1 were prepared. Also, ED
A raw material having an A / MEA ratio of 2 (molar ratio) (designated as raw material 3) and an amount of MEA (designated as raw material 4) at which the EDA / MEA ratio becomes 1 (molar ratio) when mixed with raw material 3 were prepared. . Raw material 3 was supplied to the reactor A. The reaction temperature was 300 ° C., and the reaction pressure was 50 kg / cm ² . Analysis of the reaction liquid leaving the reactor A revealed that the MEA conversion rate was 50.0%. The raw material 4 was added to this reaction liquid, and it supplied to the reactor B.
The reaction temperature was 300 ° C., and the reaction pressure was 50 kg / cm ² . When the reaction liquid exiting the reactor B was analyzed, the conversion rate of MEA was 50.1% (conversion rate of all supplied MEA). The production ratio of the polyamine excluding the raw material and the produced water was as follows: PIP: 2.92 wt%, DETA: 45.70 wt%, AEEA: 4.35 wt%, AEP: 3.64 wt%, HEP: 0.00 % By weight, TETA; 22.48
% By weight, TEPA: 10.32% by weight, PEHA: 5.
It was 97% by weight. The acyclic ratio of TETA is 8
It was 8.98%.

Example 3 A stainless steel annular reactor was charged with a catalyst (alumina carrying 20% by weight of niobium oxide). 300 this
Heated to ℃, pressure was 50kg / cm ² , EDA / M
A raw material having an EA ratio of 4 (molar ratio) was supplied. ME of reactor
MEA was supplied to the portion where the A conversion rate was 50%. ME
The amount of A supplied was such that the MEA concentration was 15.61 mol% in the reaction solution. Furthermore, the conversion rate of all MEA supplied is 4
MEA was supplied to a 3.8% portion. The amount supplied was such that the MEA concentration in the reaction solution became 19.1 mol%. Analysis of the reaction liquid leaving the reactor revealed that the conversion rate was 41.6% based on the total amount of MEA supplied. The production ratio of the polyamine excluding the raw material and the produced water is PIP: 1.37% by weight, DETA: 65.09% by weight, AEEA: 1.76.
% By weight, AEP: 1.29% by weight, HEP: 0.00% by weight, TETA; 18.40% by weight, TEPA: 4.7
It was 5% by weight and PEHA: 1.22% by weight. Note that T
The acyclic ratio of ETA was 96.41%.

Claims (1)

[Claims] 1. A method for producing polyethylene polyamine from ethanol amine and ethylene amine, wherein ethanol amine is dividedly fed to a reaction zone.